Efficient charge transport along phenylene-vinylene molecular wires

We have studied the motion of charge carriers along isolated phenylene-vinylene (PV) chains using a combination of experimental and theoretical methods. The conductive properties of positive charges along PV chains in dilute solution were studied by using the pulse-radiolysis time-resolved microwave conductivity (TRMC) technique. This technique enables the measurement of high-frequency (tens of GHz) charge carrier mobilities along isolated PV chains without the use of electrodes. The charge carrier mobility along PV chains with finite and infinite length was studied theoretically by charge transport simulations with parameters from density functional theory (DFT) calculations. The high-frequency charge carrier mobility is found to depend strongly on the conjugation length of the PV chains and is found to increase both with increasing length of the PV chain and with increasing conjugation fraction. The experimental results are in good agreement with the calculated results. On the basis of this combined experimental and theoretical study an intrachain charge carrier mobility of a few tens of cm2/Vs is expected for an infinitely long PV chain without conjugation breaks.     

High intrachain hole mobility on molecular wires of ladder-type poly(p-phenylenes)

We have studied the high-frequency (34 GHz) mobility of positive charge carriers on isolated ladder-type polymer chains in dilute solution. We find that the high-frequency mobility is limited by the chain ends on chains as long as 35 monomers. The intrachain motion of charge carriers can be described by one-dimensional diffusion between infinitely high reflecting barriers, representing the chain ends. Our data indicate that the intrachain mobility for ladder-type polymer chains is close to 600 cm(2)/V s. With this high mobility the ladder-type polymer is a promising candidate for future use as an interconnecting wire in molecular electronics.     

Location of the Spinel Vacancies in γ‐Al2O3

A non‐spinel model for the structure of γ‐Al₂O₃, with 25 % of the Al³⁺ cations at tetrahedral positions, has been the subject of wide interest. However, ¹⁷O NMR measurements and, more recently, ²⁷Al NMR measurements have shown that there are considerably more Al³⁺ cations at tetrahedral positions. This means that the Al³⁺ vacancies in γ‐Al₂O₃ are not at tetrahedral but at octahedral positions, as in isostructural γ‐Fe₂O₃ and in accordance with density functional theory predictions. This has consequences with regard to the surface structure of γ‐Al₂O₃, and thus, for catalysis.     

Direct Minimization of the least-squares spectral element functional – Part I: Direct solver

This paper describes an equivalent but improved least-squares formulation for the numerical approximation of the solution of partial differential equations. Instead of using variational analysis to impose the conditions for minimizing the residual, the residuals are minimized directly, thus leading to a method we will denote by Direct Minimization (DM). DM circumvents setting up the normal equations which consists of matrix–matrix multiplications. Matrix–matrix multiplications are expensive, may lead to loss of accuracy and destroy the sparsity pattern present in the original system. The condition number of the DM formulation is the square root of the condition number which would be obtained if variational analysis was employed. An element-by-element procedure will be presented which allows for parallelization of DM. A computational comparison between DM and the conventional least-squares formulation based on variational analysis will be presented.     

Carrier-injection-based electro-optic modulator on silicon-on-insulator with a heterogeneously integrated III-V microdisk cavity

A compact electro-optic modulator on silicon-on-insulator is presented. The structure consists of a III-V microdisk cavity heterogeneously integrated on a silicon-on-insulator wire waveguide. By modulating the loss of the active layer included in the cavity through carrier injection, the power of the transmitted light at the resonant wavelength is modulated; approximately 10 dB extinction ratio and 2.73 Gbps dynamic operation are demonstrated without using any special driving techniques.     

Boxlike filter response based on complementary photonic bandgaps in two-dimensional microresonator arrays

We propose that a boxlike filter response can be obtained by utilizing complementary photonic bandgap properties of the column and row configurations in two-dimensional microresonator arrays. The filters are fabricated using deep-UV lithography in silicon-on-insulator technology. The observed sidelobes reduction is approximately 10 dB, and the usable bandwidth can be as high as 500-750 GHz.     

Crystal and molecular structure of sodium picrate monohydrate

Na⁺ [C₆H₂(NO₂)₃O]^– H₂O,M _r=269.11, monoclinic,C2/m (No. 12),a=13.065(1),b=20.065(2),c=3.6957(4) Å,=90.75(1)°,V=968.7(1) ų,Z=4,D _m=1.848 g cm^–3 (by flotation),D _x=1.845 g cm^–3, (CuK)=1.54184 Å,(CuK)=17.5 cm^–1,F(000)=540,T=295 K,R=0.055,wR=0.060 for 879 observed reflections withI2.5(I). p]In the structure the picrate anion has exact twofold symmetry, the water molecule has exact mirror symmetry and the two sodium cations occupy special positions on inversion centers at (0, 1/2, 0) and (1/2, 1/2, 1/2). The phenyl ring together with the four substituent N and O atoms is strictly planar, but the phenyl ring is severely distorted from hexagonal symmetry, as is commonly observed in structures containing the picrate fragment. Both sodium ions are eight-coordinated with Na(1) and Na(2) in a cubic and distorted cubic arrangement, respectively. Na(1) coordinates to four charged phenoxide O atoms and four O atoms of nitro groups, and Na(2) to four O atoms of nitro groups and four water molecules. The water molecule donates two hydrogen bonds to symmetry-related O(2) atoms ofortho nitro groups. Two symmetry-related O(3) atoms ofortho nitro groups serve as acceptors in a very unusual asymmetric bifurcated C-HO hydrogen bond.     

Origin of the dendritic effect in multivalent enzyme-like catalysts

Functionalization of multivalent structures such as dendrimers and monolayer passivated nanoparticles with catalytically active groups results in very potent catalysts, a phenomenon described as the positive dendritic effect. Here, we describe a series of peptide dendrons and dendrimers of increasing generation functionalized at the periphery with triazacyclononane, a ligand able to form a strong complex with Zn(II). Kinetic studies show that these metallodendrimers very efficiently catalyze the cleavage of the RNA model compound HPNPP, with dendrimer D32 exhibiting a rate acceleration of around 80,000 (kcat/k(uncat)) operating at a concentration of 600 nM. A theoretical model was developed to explain the positive dendritic effect displayed by multivalent catalysts in general. A detailed analysis of the saturation profile and the Michaelis-Menten parameters kcat and KM shows that it is not necessary to ascribe the positive dendritic effect to, for instance, changes in the catalytic site, increased substrate binding constant, or changes in the microenvironment. Rather it appears that the efficient catalytic behavior of multivalent catalysts is mainly determined by two factors: the number of catalytic sites occupied by substrate molecules under saturation conditions, and the efficiency of the multivalent system to generate catalytic sites in which multiple catalytic units act cooperatively on the substrate.     

C3-symmetric Ti(IV) triphenolate amino complexes as sulfoxidation catalysts with aqueous hydrogen peroxide

[reaction: see text] The Ti(IV) complex 2c bearing a C3-symmetric triphenolate amine ligand is an air and moisture tolerant complex that efficiently catalyzes sulfoxidation reactions at room temperature without previous activation (catalyst loading down to 0.01%, TONs up to 8000, TOFs up to 1700 h-1, quantitative yields). Reactions were performed with aqueous hydrogen peroxide as oxidant, which adds value to the methodology from the environmental viewpoint.